Production of soda ash



Jan. 18, 1949.

E. w. CARRIER 2,459,414 PRODUCTION OF SODA ASH Filed Nov. 7, 1942 .SPnAY Selm!!! orari emula nimm;

l' "lavan I .391m Asn loader ovnzr raum lsv-Mu au can' 6 o F co As ro OHATI will Patented Jan. 18, l1949 to Standard Oil Develo poration of Delaware i PRODUCTION OFL0DA ASH ''gbert Wendell Carrier, Cranford, J., assignor pment Company, a cor- Appllcation November 7, 1942, Serial No. 464,835

2 Claims.

It has heretofore been customary in the Solvay process for the manufacture of soda ash to calcine the crude sodium bicarbonate in direct fired rotary horizontal driers. This operation is conducted with low thermal efficiency and involves large moving apparatus of relatively low capacity.

Moreover, direct red rotary driers are subject.

to uneven temperatures through the product and driershell, which promotes not only lumping of the feed, but more seriously the formation of hard scale on the internal surfaces, reducing heat transfer and enhancing the danger of overheating and warping the steel shell of the drier.v

The present invention provides a method for conducting the calcining operation with much improved fuel economy and in stationary apparatus of high capacity in which the temperature is uniform and subject to very simple and accurate control. Other and further objects of the invention will be apparent from the drawings, the following description and the claims.

Figure 1 ofthe drawings is a diagrammatic ilustration in sectional elevation of one suitable type of apparatus for carrying out the process of this invention. Figure 2 is a diagrammatic illustration' in partial sectional elevation of an apparatus suitable for carrying out another modification of the process of this invention. i

Referring to Figure `1, sodium bicarbonate is supplied by any suitable means such as the screw feeder I to a reaction vessel 2 which connects at the bottom to along standpipe 3. This sodium bicarbonate may be from any suitable source and is preferably secured from the filters of the Solvay process. In this event the particle size is fixed by the method and conditions for eii'icient precipitation and filtration, such sizes being suitable for calcining in the present Solvay process. This precipitate may be moist, or it may be dried to any desired extent before passing ,to vessel 2. It should, however, be in a finelydivided solid form, with a particle size smaller than about 60 mesh and preferably smaller than 100 mesh with not more than a minor proportion having a particle size below about 400 mesh. The reaction vessel 2 may be provided with a cylindrical partition 4 between the standpipe connection and the gas inlet line 5. It may also be provided with a perforated horizontal baille 6 in the annular space between the partition 4 and the reaction vessel wall to aid the uniform dispersal of gas and solids in the reaction vessel.

Hot gases are introduced into the lower portion of the vessel 2 by line 5 and, in passing upwardly through this vessel, maintain the solid material therein in a violently agitated state. The upward velocity of gas through vessel 2 is sufficient to partially lift the solid material and to maintain it as a dense suspension but is not sufhciently great to carry over any large proportion of solids. Thus, some settling of the suspended particles is permitted, so that a dense suspension exists in the lower portion of the reaction vessel. The upper level of this dense suspension should be a substantial distance below the top in order to reduce the amount ofvsoiids entrained in the gases leaving the reaction chamber. This distance may be from about 5 to 15 feet or more. The velocity of the gases passing upwardly through the reaction vessel 2 may be, for example, between the approximate limits of 0.2 and 5.0 feet per second, preferably between 0.5 and 2.5 feet per second at least in the upper portion of the vessel, depending upon the particle size of the solid material.A This state of violent agitation provides eflcient contact of the solids with the hot gases and greatlyaids the calcination of the sodium bicarbonate to soda ash. It

also provides a remarkably uniform temperature throughout the calcinating zone and permits close control of the temperature and the quality of the soda ash product. The calcined product is withdrawn from the vessel 2, preferably from the lower portion of this vessel insidethe baiiie 4 o1 from the standpipe 3, by line 20 and is cooled by any suitable method such as by the rotary cooler 2l and then passed to storage or to suitable packaging equipment. The cooling may also be accomplished by passing a stream of the calcined product through an externally cooled pipe 20 or heat exchanger, while providing sufcient gas preferably at spaced points along the pipe 20 to maintain the solid material as a freely flowing suspension, The product may also be Cooled by directcontact with a cooling gas, such as air, or the recycled carbon dioxide gas in line i9 before it is used t'o circulate return ash through the heater 25. Such direct contact may suitably be carried out in a vessel operated in the same man-- ner as vessel 2.

While the calciner 2 may be heated indirectly by heat applied to the walls or through heat exchanger surfaces located therein such as coils amounting to a total of about 0.5 to

for high pressure superheated steam or other heating fluids, this heating may also be done by the hot gas, suchv as recycled carbon dioxide, introduced through line or by recycling soda ash from the calciner 2 through an external heater 25. In this method of operation soda ash isv withdrawn from the vessel 2 into the standpipe 3, thus providing a long column of a solid suspension of high density. A sumcient amount of a gas. such as the recycled carbon dioxide, is supplied at spaced points along this column as by line" 22 to maintain the solid material in a mobile or suspended state. This can be accomplished with a relatively small amount of gas, 5.0 cubic feet per 100 pounds of ash measured under the conditions of highest pressure prevailing at the bot `om of the column. In many cases, especially where the solids arerecirculatedat relatively high rates, the amount of gas occluded in the solids leaving thereaction zone may be sufllcient to maintain it in a fluidized state without adding additional gas to the column. When operating in this manner with finely powdered solids, each particle of solid appears to be surrounded by a thin illm of'gas and the entire mass has the mobility of a freely flowing liquid. Also, itfollows the hydraulic laws in generating a pressure at any point equal to the product of the average density and the height of the suspension. Return flow to the top of the standpipe vis thus made possible simply by providing enough additional gas to maintain a lower 'density in the return side of the cycle, the cycle operating in a manner analogous to a liquid thermO-syphon. Thus,'the iluidized solid is released Vat acontrolled rate through valve 23, at l'.he'b1.)ttom of the standpipe 3, into a stream of gas, suitably a recycled carbon dioxide gas from the calciner products, in line 24 to provide a more dilute suspension of solids in line 24 than in standpipe 3. The pressure in line 24 is less than that just above valve 23. This stream in line 24 is passed through suitable heating equipment such as the furnace-fired heat exchanger 25 and is heated.` therein lto a temperature substantially higher than the temperature desired in the calciner 2. The heated suspension is then returned to the calciner by line 5. A final heating of all or a portion of the suspension in the radiant heater 26 may be used to complete the introduction of heat or for more accurate and ecient temperature control.

' Gases liberated during drying and decomposition of the crude sodium bicarbonate as well as recycle gases are withdrawn from the vessel 2 by line 1 after passing through suitable solids separating equipment such as the cyclone type separatorg28 which may be conveniently disposed inside the top of the reaction vessel or it may be placed in the gas exit line outside' this vessel. Several stages of separators may of course be used in series to increase the eiciency of the solids separation. The separated solids are preferably returned to the reaction vessel or to the solids recycle system as by line 9.

The gases leaving the reaction vessel contain ammonia in addition to carbon dioxide and water' vapor and are passed through suitable cooling, scrubbing, condensing and water washing equipment to separate water and ammonia from the carbon dioxide gas. The hot gas may, for example, be passed through a spray scrubber 8 in which it is cooled and scrubbed by being passed through a spray of liquid. suitably the ltrate or 4 filter liquor" obtained from the' sodium bicarbonate filters of the Solvay process by line l0. The gas may then be passed by line Il through an externally cooled condenser I2 and the resulting condensate together with the wash liquor from the spray scrubber 8 are withdrawn by line i3 to the Solvay distillers for 'the recovery of ammonia. The cooled gas is then passed countercurrent to water or other suitable solvent in scrubbing tower Il for the further recovery of ammonia, the enriched solvent being passed by line l5 to the Solvay weak liquor distillers forV ammonia recovery. The resulting gas which is carbon dioxide of 90% or higher concentration is passed by line I8 to compressors l1, which are ordinarily used toreturn the carbon dioxide to the carbonating towers of the Solvay process by line I8. A part of `this compressed gas.is used as recycle gas to circulate the solids in the improved vcalcining operation and is continuously returned through line I9, which connectsv with the bottom of the standpipe 3.

Figure 2 illustrates an alternate type of calcining vessel 32 which may be used in place of the calciner-2 in Figure 1. Parts which are the same as in Figure 1 are indicated bythe same numbers. The chief difference is that the vessel 32 is designed for all solids and gases to be taken overhead through line Il to`a separating means Ill) 38 which maybe a` cyclone separator; a number of such separators in series followed byla Cottrell type precipitator, or other suitable means for separating the finely divided solids fromy the gas. Higher gas velocities, ranging from 0.2 to feet per second, may be used in this type vof reac tion vessel,v velocities ofl about 0.5.to 5.()l feet per second being generally preferred.v The gases are passed from such separating means through line 1 to suitable cooling and ammonia recovery equipmentA as illustrated in Figure 1'.

through heater 25. Calcined material may also be withdrawn to 'storage through line 20, as in Figure 1. The crude sodium bicarbonate is supplied to the calciner as in Figure 1 by. a screw conveyer 3| or other suitable feeding means. The gases supplied through line 5 are passed upwardly through the vessel 32 at a sufiicient velocity to maintain the solids therein in a mobile suspended state although preferably the velocity is sufllcientn ly low to permit much slippage between solids and the gas anda much longer average time of.

residence of solids, than of gas, in the vessel l32. However. the upward'gas velocity may be considerably higher than in vessel 2. vThe density off heating may also be accomplished by burning f -uel A combustibleA mix-- in the reaction vessel 32. ture of fuel gas, oil or powdered coal andair may be supplied through line 39 or the combustiblev material and air may be supplied separately to the reaction vessel 32 by lines 40. However, the purity of the product will generally be lower when heating by such direct contact with combustible materials and the -recovery of ammonia involves washing a greater volume of gas.' In

The separated solids pass into the standpipe 33 for recycling Y cubic foot. y the standpipe (per parts. of recycle) is withorder to avoid undesirable dilution `of'the resulting carbon dioxide gas excess air should-not be lused for the direct combustion.

As an example of the process of thisinvention :involving apparatus as illustrated in Figure l,

crude sodium bicarbonate vmay be supplied'directly .from Solvay. process 4rotary vacuum iilters to a calciner 11 feet in. diameter and 40 feet high connecting with a standpipe`50 `feet in height. The

operation is preferably started with .a Ahot, charge of previously manufacturedA soda ash in the calciner for recycling and heating (although the crude bicarbonate might Abe .heated in the calciner, withoutrecycling, lby passing 4ho't gas through it). Continuous operation may be obtained by maintaining the temperature in the calciner at about 400 F. and allowing 25 minutes solid contact -time to complete the decomposition.

Heat is supplied lduring continuous operation by recycling 5 parts of return ash from the" standpipe per part of soda ash product. Thereturn ash is suspended in recycled 'concentrated carbon-dioxide gas which amounts to 25-3 O% of that generated by decomposition of the crude ,bicarf bonatefeed and vreturned to the carbonating towers. The return ash suspension is superheated to about 820 F. in a vertical tubular heater and thence'ilows vat this temperature into Y thebottom of the calciner. A gas velocity of 0.5

vfoot per second up through the calciner gives a concentration of solids in thedenSe, lower portion ofthe dispersion of about 20 pounds per One part of the ash passing into drawn and cooled to about 175 F. before packaging ors'torage as product. Operating in the manner described, this calciner will have a prod-- uct capacity exceeding 120 tons of soda ash per day, or over twicev the capacity of former direct -red rotary horizontal driers.

It will be understood that the upward gas velocity in the calciner and the proportion of recycled material to product withdrawn may be adjusted to provide any desired time of contact and tosecure decompositionoi the sodium bicarbonate to soda ash to any extent desired. If, however, under the conditions shown in the fore going example the soda ash product is contaminated with too much undecomposed bicarbonate (more than 0.5%), the product canbe further dried by running through one or more additional calciners in series operating on the same principle.

It is also to be understood that while the above.

description is intended to present preferred em-l bodiments of the process or this invention, it also includes suchother variations and modifications as come within the scope thereof.

- For example the calciners of Figure 1 or 2 might be employed in an adaption ofthis process to the preparation of so-called "dense ash, in which about 16 per cent of water is mixed with light soda ash of about 0.54 bulk density, then fed in place of crude bicarbonate into the calciner, and dried by means of superheated return ash-gas suspension. The resulting dense ash would have a bulk density of 0.95-1.0, and has special uses as in glass manufacture.

I claim:

1. Process'for the manufacture of soda ash, which comprises maintaining a fluidized mass of previously'manufactured soda ash in a rising Icarbon dioxide gas stream Within a confined reaction zone, introducing sodium bicarbonate into. said reaction zone, decomposing said bicarbonate while in said zone into soda, ash, carbon dioxide and water Vapor, withdrawing soda ash solids from said reaction zone, separating the soda ash solids withdrawn from lthe `reaction zone into two streams, heating one of said streams to a tcmperature substantially higher than the temperaaction zone. EGBERT WENDELL CARRIER.

REFERENCES CITED The following references vare of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 243,991 Solvay July 5, 1881 263,281 Solvay Sept. 5, 1.882 439,330 Staub Oct. 28, 1890 1,984,380 Odell Dec. 18, 1934 2,055,084 MacMillin Sept. 22, 1936 2,311,564 Munday Feb. 16, 1943 2,373,008

Becker Apr. 3, 1945 

